2-(3-ethanesulfonylpyridine-2-yl)-5-(trifluoromethanesulfonyl) benzoxazole crystal

ABSTRACT

A type 2 crystal of 2-(3-ethanesulfonylpyridin-2-yl)-5-(trifluoromethanesulfonyl)benzoxazole having diffraction peaks at 2θ=14.0±0.2°, 14.3±0.2°, 16.5±0.2°, 16.9±0.2°, 17.6±0.2°, 18.8±0.2°, 19.9±0.2°, and 22.3±0.2° in powder X-ray diffraction using Cu-Kα radiation is a stable crystal.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Section 371 of International Application No.PCT/JP2016/086849, filed Dec. 12, 2016, which was published in theJapanese language on Jun. 22, 2017, under International Publication No.WO 2017/104592 A1, which claims priority under 35 U.S.C. § 119(b) toJapanese Patent Application No. 2015 244909, filed on Dec. 16, 2015, thedisclosures of which are incorporated herein by reference in theirentireties.

TECHNICAL FIELD

The present invention relates to a crystal of2-(3-ethanesulfonylpyridin-2-yl)-5-(trifluoromethanesulfonyl)benzoxazole(hereinafter referred to as “Compound (1)”)

represented by the following formula (1)

having control efficacies against pests.

BACKGROUND ART

WO 2014/104407 describes that the Compound (1) has control efficaciesagainst pests.

The crystal of the Compound (1) produced in Preparation Example 3 andPreparation Example 17(5) in WO 2014/104407 is a crystal havingdiffraction peaks at 2θ=13.7±0.2°, 16.2±0.2°, 16.6±0.2°, 17.1±0.2°,18.8±0.2°, 20.2±0.2°, 21.4±0.2°, and 27.6±0.2° in powder X-raydiffraction using Cu-Kα radiation (hereinafter referred to as “type 1crystal”), and having diffraction peaks as shown in Table 1.

TABLE 1 2θ value (°) d value (Å) Relative intensity (%) 13.7 6.4586 25.616.1 5.5075 22.8 16.6 5.3235 35.1 17.1 5.1872 22.3 18.8 4.7111 16.6 20.24.3968 56.4 21.4 4.1448 100 27.6 3.2338 44.6

SUMMARY OF THE INVENTION

The present invention provides a more stable crystal of the Compound(1).

The Compound (1) has various crystal forms, and several crystals whichare different from one another in the crystal form may be produced byappropriately selecting the solvent used in recrystallization or thetemperature in crystallization (for example, Reference Examples 1 to 3).According to the present invention, a crystal having diffraction peaksat 2θ=14.0±0.2°, 14.3±0.2°, 16.5±0.2°, 16.9±0.2°, 17.6±0.2°, 18.8±0.2°,19.9±0.2°, and 22.3±0.2° (hereinafter referred to as “type 2 crystal”)is a stable crystal of the Compound (1).

Using a stable crystal can prevent the decrease in the controlefficacies against pests.

A type 2 crystal may be produced by dissolving a type 1 crystal into2-propanol, followed by precipitating a crystal at the temperature of 65to 67° C.

Alternatively, a type 2 crystal may also be produced by crystallizationfrom a solvent other than 2-propanol (for example, a mixed solvent ofxylene and n-heptane) when a seed crystal of type 2 crystal is present.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows powder X-ray diffraction of a type 1 crystal of theCompound (1).

FIG. 2 shows powder X-ray diffraction of a type 2 crystal of theCompound (1).

FIG. 3 shows powder X-ray diffraction of a type 3 crystal of theCompound (1).

FIG. 4 shows powder X-ray diffraction of a type 4 crystal of theCompound (1).

FIG. 5 shows powder X-ray diffraction of a type 5 crystal of theCompound (1).

DESCRIPTION OF EMBODIMENTS

In the present description, the conditions for the powder X-raydiffraction are as follows.

(Measurement Conditions)

-   Device for powder X-ray diffraction: SmartLab (manufactured by    Rigaku Corporation)-   X-ray output: CuKα, 45 kV, 200 mA-   Sampling interval: 0.02°-   Scan range: 5° to 50°

A type 1 crystal may be produced by concentrating a solution of theCompound (1) in ethyl acetate or chlorobenzene under reduced pressure,followed by drying the resulting residues.

Alternatively, a type 1 crystal may also be produced by adding a poorsolvent such as n-heptane to a solution of the Compound (1) in xylene,followed by cooling the resulting mixture.

The present invention relates to a type 2 crystal which is a more stablecrystal of the Compound (1). A specific method for producing a type 2crystal is described below with examples.

-   1) Type 1 crystals (1 part by weight) are completely dissolved into    2-propanol (6 to 7 parts by weight) at 70° C. to 82° C.-   2) The above solution at 70° C. to 82° C. is gradually cooled (for    example, at the rate of 3° C./hr) to precipitate crystals at 65° C.    to 67° C. If a crystal is not precipitated, a part of 2-propanol may    be evaporated to reduce the amount of 2-propanol, and then the    solution may be gradually cooled again.-   3) The precipitated crystals are filtered and dried to produce type    2 crystals.

A type 2 crystal may also be produced by adding a seed crystal of type 2crystal to a supersaturated solution of the Compound (1), followed bymaintaining the same temperature or gradually cooling the solution (forexample, at the rate of 3° C./hr). Examples of the solvent to be used inthe crystallization include 2-propanol, a mixed solvent of xylene andn-heptane in a weight ratio of 1:1, and a mixed solvent of xylene andn-heptane in a weight ratio of 7:3. The temperature for precipitating acrystal is 55° C. to 82° C.

Also, the amount of the solvent in precipitating a type 2 crystal isusually within a range of 3 to 20 parts by weight relative to 1 part byweight of the Compound (1).

The amount of the seed crystal used in producing a type 2 crystal isusually 0.001 to 10% by weight, preferably 0.005 to 1% by weightrelative to 1 part by weight of the Compound (1).

A pesticide formulation comprising a type 2 crystal (hereinafterreferred to as “present pesticide formulation”) is more stable than apesticide formulation comprising a crystal having another crystal formof the Compound (1).

The present pesticide formulation comprises a type 2 crystal and aninert carrier. Examples of the inert carrier include solid carriers andliquid carriers.

Examples of the solid carriers include fine powders or granules of clays(for example, kaolin clay, diatomaceous earth, bentonite, Fubasami clay,pyrophyllite clay, or acid white clay), synthetic hydrated siliconoxide, talc, ceramics, other inorganic minerals (for example, sericite,quartz, sulfur, active carbon, calcium carbonate, or hydrated silica),solids for fertilizer (for example, ammonium sulfate, ammoniumphosphate, ammonium nitrate, urea, or ammonium chloride), and theothers. Examples of the liquid carriers include water and aliphatichydrocarbons (for example, kerosene or light oil).

Examples of the pests which may be controlled by the present pesticideformulation include harmful arthropods (for example, harmful insects orharmful acarina), harmful mollusks (for example, harmful Gastropoda),and harmful Nematoda (nematode), and the specific examples thereofinclude the followings.

-   Hemiptera pests: Laodelphax striatellus, Nilaparvata lugens,    Sogatella furcifera, Nephotettix cincticeps, Nephotettix virescens,    Empoasca onukii, Aphis gossypii, Myzus persicae, Brevicoryne    brassicae, Aphis spiraecola, Macrosiphum euphorbiae, Aulacorthum    solani, Rhopalosiphum padi, Toxoptera citricidus, Hyalopterus pruni,    Nezara antennata, Eysarcoris parvus, Halyomorpha mista, Riptortus    clavetus, Leptocorisa chinensis, Trigonotylus caelestialium,    Stenotus rubrovittatus, Trialeurodes vaporariorum, Bemisia tabaci,    Dialeurodes citri, Aleurocanthus spiniferus, Aonidiella aurantii,    Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens, Icerya    purchasi, Planococcus kraunhiae, Pseudococcus longispinis,    Pseudaulacaspis pentagona, Diaphorina citri, Psylla pyrisuga,    Bactericerca cockerelli, Stephanitis nasi, Cimex lectularius, and    the others.-   Lepidoptera pests: Chilo suppressalis, Tryporyza incertulas,    Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella,    Ostrinia furnacalis, Hellula undalis, Pediasia teterrellus,    Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra    brassicae, Agrotis Ipsilon, Plusia nigrisigna, Pieris rapae,    Grapholita molesta, Leguminivora glycinivorella, Matsumuraeses    azukivora, Adoxophyes orana fasciata, Adoxophyes honmai., Homona    magnanima, Archips fuscocupreanus, Cydia pomonella, Caloptilia    theivora, Phyllonorycter ringoneella, Carposina niponensis, Plutella    xylostella, Pectinophora gossypiella, Phthorimaea operculella,    Hyphantria cunea, and the others.-   Thysanoptera pests: Frankliniella occidentalis, Thrips parmi,    Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa, and the    others.-   Diptera pests: Delia platura, Delia antiqua, Agromyza oryzae,    Hydrellia griseola, Liriomyza sativae, Liriomyza trifolii,    Chromatomyia horticola, Chlorops oryzae, Dacus cucurbitae, Ceratitis    capitata, Megaselia spiracularis, Clogmia albipunctata, and the    others.-   Coleoptera pests: Diabrotica virgifera virgifera, Diabrotica    undecimpunctata howardi, Oulema oryzae, Aulacophora femoralis,    Phyllotreta striolata, Leptinotarsa decemlineata, Anomala cuprea,    Anomala rufocuprea, Popillia japonica, Sitophilus zeamais,    Echinocnemus squameus, Lissorhoptrus oryzophilus, Sphenophorus    venatus, Anthonomus grandis, Epilachna vigintioctopunctata, Lyctus    brunneus, Tomicus piniperda, Anoplophora malasiaca, Agriotes ogurae    fuscicollis, Agriotes spp., Paederus fuscipes, and the others.-   Orthoptera pests: Locusta migratoria, Gryllotalpa africana, Oxya    yezoensis, Oxya japonica, and the others.-   Hymenoptera pests: Athalia rosae, Athalia japonica, and the others.-   Termitidae pests: Reticulitermes speratus, Coptotermes formosanus,    Incisitermes minor, Cryptotermes domesticus, Odontotermes    formosanus, Neotermes koshunensis, Glyptotermes satsumensis,    Glyptotermes nakajimai, Glyptotermes fuscus, Glyptotermes kodamai,    Glyptotermes kushimensis, Hodotermopsis japonica, Coptotermes    guangzhoensis, Reticulitermes miyatakei, Reticulitermes flaviceps    amamianus, Reticulitermes sp., Nasutitermes takasagoensis,    Pericapritermes nitobei, Sinocapritermes mushae, and the others.-   Acarina pests: Tetranychus urticae, Tetranychus kanzawai, Panonychus    citri, Panonychus ulmi, Aculops pelekassi, Phyllocoptruta citri,    Aculops lycopersici, Calacarus carinatus, Acaphylla theavagrans,    Eriophyes chibaensis, Aculus schlechtendali, Polyphagotarsonemus    latus, Brevipalpus phoenicis, Tyrophagus putrescentiae, Tyrophagus    similis, Dermatophagoides farinae, Dermatophagoides ptrenyssnus, and    the others.-   Chilopoda: Thereuonema hilgendorfi, Scolopendra subspinipes, and the    others.-   Diplopoda: Oxidus gracilis, Nedyopus tambanus, and the others.-   Isopoda: Armadillidium vulgare and the others.-   Gastropoda: Limax marginatus, Limax flavus, and the others.-   Nematoda: Aphelenchoides besseyi, Nothotylenchus acris, Meloidogyne    incognita, Meloidogyne hapla, Meloidogyne javanica, Heterodera    glycines, Globodera rostochiensis, Pratylenchus coffeae,    Pratylenchus neglectus, and the others.

Examples of the present pesticide formulation include dosage formsclassified as Aqueous suspension concentrates, Wettable powders, Waterdispersible granules, or Granules.

Examples of the method for controlling pests using the present pesticideformulation include a method comprising applying an effective amount ofthe present pesticide formulation to the foliage of plants or the soilwhere plants are cultivated, and the specific examples thereof includetreatment to the foliage of plant such as foliage application, soiltreatment, and treatment to plantations of plants such as hydroponicsolution treatment. The present pesticide formulation is applied once ortwo or more times.

Specific examples of the treatment to the foliage of plants includetreatment methods comprising applying the present pesticide formulationto surfaces of plants such as foliage application and stem application.Examples of the soil treatment include spraying to soil, soilincorporation, and drenching soil with liquid chemicals. Examples of theplace to be treated include planting holes, planting rows, the vicinityof planting holes, the vicinity of planting rows, the entire area ofplantation, basal parts of plants, inter-row spaces, places under thestems, ridges between main stems, culture soil, seedling boxes, seedlingtrays, and seedbeds. Examples of the timing of the treatment includeduring pre-seeding stages, seeding stages, stages immediately afterseeding, and during the growing periods including seedling raisingstages, pre-planting stages, planting stages, and post-planting stages.Examples of hydroponic solution treatment include injection intoirrigation facilities (an irrigation tube, an irrigation pipe, asprinkler, and the like), incorporation into a liquid for inter-rowspace irrigation, and incorporation into a hydroponic solution.

When the present pesticide formulation is used for controlling pests,the application dose of the type 2 crystal is usually 1 to 10,000 g per10,000 m². Aqueous suspension concentrates or the like are usuallyapplied by diluting it with water in such a way that a concentration ofthe type 2 crystal is within a range of 0.01 to 10,000 ppm.

When the present pesticide formulation is applied to paddy rice, theapplication dose of the type 2 crystal is usually 0.1 to 10 g per aseedling box (inner dimension: 28 cm×58 cm). The type 2 crystal isapplied by diluting it with water in such a way that the concentrationthereof is within a range of 0.01 to 10,000 ppm, or the presentpesticide formulation is directly applied to a seedling box.

The present pesticide formulation may be used in farm land where variousplants are cultivated. For example, the present pesticide formulation orits dilution with water may be used in farm land where the followingplants are cultivated.

-   Crops: corn, rice, wheat, barley, rye, oat, sorghum, cotton,    soybean, peanut, buckwheat, beet, rapeseed, sunflower, sugar cane,    tobacco, and the others;-   Vegetables: solanaceous vegetables (for example, eggplant, tomato,    pimento, pepper, or potato), cucurbitaceous vegetables (for example,    cucumber, pumpkin, zucchini, water melon, or melon), cruciferous    vegetables (for example, Japanese radish, white turnip, horseradish,    kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, or    cauliflower), asteraceous vegetables (for example, burdock, crown    daisy, artichoke, or lettuce), liliaceous vegetables (for example,    welsh onion, onion, garlic, or asparagus), ammiaceous vegetables    (for example, carrot, parsley, celery, or parsnip), chenopodiaceous    vegetables (for example, spinach or Swiss chard), lamiaceous    vegetables (for example, perilla, mint, or basil), strawberry, sweet    potato, glutinous yam, eddoe, and the others;-   Fruits: pomaceous fruits (for example, apple, pear, Japanese pear,    Chinese quince, or quince), stone fleshy fruits (for example, peach,    plum, nectarine, Japanese apricot (Prunus mume), cherry fruit,    apricot, or prune), citrus fruits (for example, Citrus unshiu,    orange, lemon, lime, or grapefruit), nuts (for example, chestnuts,    walnuts, hazelnuts, almond, pistachio, cashew nuts, or macadamia    nuts), berry fruits (for example, blueberry, cranberry, blackberry,    or raspberry), grapes, Japanese persimmon, olive, Japanese plum,    banana, coffee, date palm, coconuts, oil palm, and the others;-   Trees other than fruit trees: tea, mulberry, flowering plants (for    example, Satuki azalea (Rhododendron indicum), camellia, hydrangea,    sasanqua, skimmia, cherry, tulip tree, crape myrtle, or orange    osmanthus), roadside trees (for example, ash, birch, dogwood,    eucalyptus, ginkgo (ginkgo biloba), lilac, maple, oak (quercus),    poplar, Judas tree, Formosan gum (Liquidambar formosana), plane    tree, zelkova, Japanese arborvitae (Thuja standishii), fir wood,    hemlock, juniper, pinus, picea, yew (Taxus cuspidate), elm, or    buckeye), sweet viburnum, shrubby Japanese yew (Podocarpus    macrophyllus), Japanese cedar, hinoki cypress, croton, Japanese    spindle tree (Euonymus japonicus), Japanese photinia (Photinia    glabra), and the others;-   Turfgrass: Zoysia (for example, zoysiagrass (Zoysia japonica) or    Korean lawn grass (Zoysia tenuifolia)), Cynodon (for example,    bermuda grass), Agrostis (bentgrasses) (for example, creeping    bentgrass (Agrostis alba), Agrostis stolonifera, or Agrostis    capillaris), Poa (blueglasses) (for example, Kentucky bluegrass or    rough bluegrass), Festuca (for example, tall fescue (Festuca    arundinacea), chewing fescue (Festuca rubra var. commutata), or    creeping red fescue (Festuca rubra var.)), Lolium (ryegrasses) (for    example, Italian ryegrass or perennial ryegrass), orchard grass,    timothy, and the others;-   Other plants: Flowers (for example, rose, carnation, chrysanthemum,    showy prairie gentian, annual baby's breath, gerbera, marigold,    salvia, petunia, verbena, tulip, aster, gentian, lily, pansy,    cyclamen, orchid, lily of the valley, lavender, stock, ornamental    cabbage, primula, poinsettia, gladiolus, cattleya, daisy, cymbidium,    or begonia), biofuel plants (for example, Jatropha, curcas,    safflower, Camelina, switchgrass, miscanthus, reed canary grass,    giant reed, kenaf, cassava, willow, or algae), foliage plants, and    the others.

The above plants also include genetically engineered plants.

The present pesticide formulation may be mixed with or used incombination with other insecticides, acaricides, nematicides,fungicides, herbicides, synergists, safeners, or plant growthregulators. For example, the present pesticide formulation may be mixedwith or used in combination with the active ingredients of the followinginsecticides, acaricides, nematicides, fungicides, herbicides,synergists, safeners, or plant growth regulators.

Active ingredients of insecticides, acaricides, or nematicides

-   (1) Organophosphorus Compounds

acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos,chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos,chlorpyrifos-methyl, coumaphos, cyanophos (CYAP), demeton-S-methyl,diazinon, dichlorvos (DDVP), dicrotophos, dimethoate, dimethylvinphos,disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion(MEP), fenthion (MPP), heptenophos, isofenphos,isopropyl-O-(methoxyaminothiophosphoryl)salicylate or isocarbophos,isoxathion, malathion, mecarbam, methamidophos, methidathion (DMTP),mevinphos, monocrotophos, naled (BRP), omethoate, oxydemeton-methyl,parathion, parathion-methyl or methyl parathion, phenthoate (PAP),phorate, phosalone, phosmet (PMP), phosphamidon, phoxim,pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos,pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos,tetrachlorvinphos, thiometon, triazophos, trichlorfon (DEP), andvamidothion;

-   (2) Carbamate Compounds

alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim,butoxycarboxim, carbaryl (NAC), carbofuran, carbosulfan, ethiofencarb,fenobucarb (BPMC), formetanate, furathiocarb, isoprocarb (MIPC),methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur (PHC),thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb;

-   (3) Synthetic Pyrethroid Compounds

acrinathrin, allethrin, bifenthrin, bioallethrin, bioresmethrin,cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin,deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin,fenvalerate, flucythrinate, flumethrin, fluvalinate, tau-fluvalinate,halfenprox, heptafluthrin, imiprothrin, kadethrin, meperfluthrin,momfluorothrin, permethrin, phenothrin, prallethrin, pyrethrins,resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethylfluthrin,tralomethrin, and transfluthrin;

-   (4) Nereistoxin Compounds

bensultap, cartap, cartap hydrochloride, thiocyclam, thiosultap-disodiumor bisultap, and thiosultap-monosodium or monosultap;

-   (5) Neonicotinoid Compounds

acetamiprid, clothianidin, dinotefuran, flupyradifurone, imidacloprid,nitenpyram, sulfoxaflor, thiacloprid, and thiamethoxam;

-   (6) Benzoylurea Compounds

bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron,flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron,teflubenzuron, and triflumuron;

-   (7) Phenylpyrazole Compounds

ethiprole, fipronil, and flufiprole;

-   (8) Hydrazine Compounds

chromafenozide, halofenozide, methoxyfenozide, and tebufenozide;

-   (9) Organochlorine Compounds

chlordane, endosulfan, and alpha-endosulfan;

-   (10) Diamide Compounds

chlorantraniliprole, cyantraniliprole, cycloniliprole, flubendiamide,and tetraniliprole;

-   (11) Natural Insecticides

machine oil, nicotine-sulfate, and rotenone;

-   (12) Microbial Materials

raw spores derived from Bacillus thuringiensis, var. aizawai, var.kurstaki, var. israelensis, or var. tenebriosis, produced crystal toxinsthereof, and mixtures thereof, Bacillus sphaericus, Beauveria bassiana(for example, strain GHA), Beauveria brongniartii, Paecilomycesfumosoroseus, Paecilomyces lilacinus, Paecilomyces tenuipes, Trichodermaharzianum, and Verticillium lecani;

-   (13) Nematicidal Active Compounds

dazomet, fluensulfone, fosthiazate, imicyafos, metam, potassiumantimonyl tartrate trihydrate, tioxazafen, Arthrobotrys dactyloides,Bacilus firmus (for example, strain 1-1582), Bacillus megaterium,Hirsutella rhossiliensis, Hirsutella minnesotensis, Monacrosporiumphymatopagus, Pasteuria nishizawae, Pasteuria penetrans, Pasteuriausgae, Verticillium chlamydosporium, and Harpin protein;

-   (14) Other Acaricidal Active Compounds

acequinocyl, amitraz, benzoximate, bifenazate, bromopropylate,chinomethionat, clofentezine, cyenopyrafen, cyflumetofen, cyhexatin ortricyclohexyltin hydroxide, dicofol, etoxazole, fenazaquin, fenbutatinoxide, fenpyroximate, fluacrypyrim, fluazuron, flufenoxystrobin,hexythiazox, propargite (BPPS), pyflubumide, pyridaben, pyrimidifen,pyriminostrobin, spirodiclofen, spiromesifen, tebufenpyrad, andtetradifon;

-   (15) Other Insecticides

abamectin, emamectin-benzoate, lepimectin, milbemectin, spinetoram,spinosad, afidopyropen, aluminium phosphide, calcium phosphide,phosphine, zinc phosphide, azadirachtin, buprofezin, chlorfenapyr,chloropicrin, cyromazine, diafenthiuron, DNOC, fenoxycarb, flometoquin,flonicamid, hydramethylnon, hydroprene, indoxacarb, kinoprene,metaflumizone, methoprene, methoxychlor, methyl bromide, metoxadiazone,pymetrozine, pyrazophos, pyridalyl, pyrifluquinazone, pyriproxyfen,sodium aluminium fluoride or chiolite, spirotetramat, sulfluramid,sulfuryl fluoride, tolfenpyrad, and triflumezopyrim.

Active Ingredients of Fungicides

-   (1) DMI Fungicides (Demethylation Inhibitors)

azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole,diniconazole, diniconazole-M, epoxyconazole, etaconazole, fenarimol,fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole,imazalil, imibenconazole, ipconazole, metconazole, myclobutanil,nuarimol, oxpoconazole, oxpoconazole fumarate, pefurazoate, penconazole,prochloraz, propiconazole, prothioconazole, pyrifenox, pyrisoxazole,simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol,triflumizole, triforine, and triticonazole;

-   (2) Amine Fungicides

aldimorph, dodemorph, fenpropidin, fenpropimorph, piperalin,spiroxamine, and tridemorph;

-   (3) Benzimidazole Fungicides

benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate, andthiophanate-methyl;

-   (4) Dicarboximide Fungicides

chlozolinate, iprodione, procymidone, and vinclozolin;

-   (5) Anilinopyrimidine Fungicides

cyprodinil, mepanipyrim, and pyrimethanil;

-   (6) Phenylpyrrole Fungicides

fenpiclonil and fludioxonil;

-   (7) QoI Inhibitors

azoxystrobin, coumoxystrobin, dimoxystrobin, enoxastrobin, famoxadone,fenamidone, fenaminstrobin, flufenoxystrobin, fluoxastrobin,kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin,picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin,pyribencarb, triclopyricarb, trifloxystrobin, andN-methyl-2-[2-(2,5-dimethylphenoxy)methyl]phenyl-2-methoxyacetamide(including a racemate or an enantiomer, and a mixture of an arbitraryratio of R-enantiomer and S-enantiomer);

-   (8) PA Fungicides (Phenyl Amide Fungicides)

benalaxyl, benalaxyl-M or kiralaxyl, furalaxyl, metalaxyl, metalaxyl-Mor mefenoxam, oxadixyl, and ofurace;

-   (9) Carboxylic Acid Amide Fungicides

dimethomorph, flumorph, pyrimorph, benthiavalicarb,benthivalicarb-isopropyl, iprovalicarb, mandipropamid, and valifenalate;

-   (10) SDHI Fungicides

benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram,fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, isopyrazam,mepronil, oxycarboxin, penthiopyrad, penflufen, sedaxane, thifluzamide,and a compound represented by the following formula (a);

-   (11) Dithiocarbamate Fungicides

ferbam, mancozeb or manzeb, maneb, metiram, propineb, thiram, zineb, andziram;

-   (12) MBI-R agents

phthalide or fthalide, pyroquilone, and tricyclazole;

-   (13) MBI-D agents

carpropamide, diclocymet, and fenoxanil;

-   (14) Microbial Materials

Agrobacterium radiobactor (for example, strain 84), Bacillusamyloliquefaciens, Bacillus pumulus, Bacillus simplex (for example,strain CGF2856), Bacillus subtilis (synonyms for Bacillusamyloliquefaciens) (for example, strain QST713, strain FZB24, strainMBI600, strain D747, strain HAI0404, or strain Y1336), Variovoraxparadoxus (for example, strain CGF4526), Erwinia carotovora (forexample, strain CGE234M403), Pseudomonas fluorescens (for example,strain G7090), Talaromyces flavus (for example, strain SAY-Y-94-01), andTrichoderma atroviride (for example, strain SKT-1);

-   (15) Other Fungicides

acibenzolar-S-methyl, ametoctradin, amisulbrom, anilazine, biphenyl,blasticidin-S, bupirimate, captafol, captan, chinomethionat orquinomethionate, chloroneb, chlorothalonil, cyazofamid, cyflufenamid,cymoxanil, dichlofluanid, diclomezine, dicloran, diethofencarb,diflumetorim, dimethirimol, dinocap, dithianon, dodine, echlomezol oretridiazole, edifenphos, ethaboxam, ethirimol, fenhexamid,fenpyrazamine, fentin acetate, fentin chloride, fentin hydroxide,ferimzone, fluazinam, fluopicolide, fluoroimide, flusulfamide,flutianil, folpet, fosetyl, guazatine, hymexazol, iminoctadine,iminoctadine triacetate, iodocarb, iprobenfos, isoprothiolane,isotianil, kasugamycin, laminarin, meptyldinocap, methasulfocarb,metrafenone, octhilinone, oxathiapiprolin, oxolinic acid,oxytetracycline, pencycuron, polyoxins, probenazole, propamocarb,proquinazid, prothiocarb, pyrazophos, pyributicarb, pyriofenone,quinoxyfen, quintozene, streptomycin, tebufloquin, tecloftalam,tecnazene, tiadinil, tolclofos-methyl, tolfenpyrad, tolylfluanid,tolprocarb, triazoxide, validamycin A, zoxamide, basic copper chloride,copper(II) hydroxide, basic copper sulfate, organic copper, sulfur,3-chloro-5-phenyl-6-methyl-4-(2,6-difluorophenyl)pyridazine,3-cyano-5-phenyl-6-methyl-4-(2,6-difluorophenyl)pyridazine,N-(1,1,3-trimethylindan-4-yl)-1-methyl-3-difluoromethylpyrazole-4-carboxylicacid amide (including a racemate or an enantiomer, and a mixture of anarbitrary ratio of R-enantiomer and S-enantiomer); a compoundrepresented by the following formula (b);

a compound represented by the following formula (c);

and a compound represented by the following formula (d);

Active Ingredients of Herbicides

-   (1) Phenoxy Fatty Acid Herbicidal Compounds:

2,4-PA, MCP, MCPB, phenothiol, mecoprop, fluroxypyr, triclopyr,clomeprop, and naproanilide.

-   (2) Benzoic Acid Herbicidal Compounds:

2,3,6-TBA, dicamba, clopyralid, picloram, aminopyralid, quinclorac, andquinmerac.

-   (3) Urea Herbicidal Compounds:

diuron, linuron, chlortoluron, isoproturon, fluometuron, isouron,tebuthiuron, methabenzthiazuron, cumyluron, daimuron, andmethyl-daimuron.

-   (4) Triazine Herbicidal Compounds:

atrazine, ametoryn, cyanazine, simazine, propazine, simetryn,dimethametryn, prometryn, metribuzin, triaziflam, and indaziflam.

-   (5) Bipyridinium Herbicidal Compounds:

paraquat and diquat.

-   (6) Hydroxybenzonitrile Herbicidal Compounds:

bromoxynil and ioxynil.

-   (7) Dinitroaniline Herbicidal Compounds:

Pendimethalin, Prodiamine, and Trifluralin.

-   (8) Organophosphorus Herbicidal Compounds:

amiprofos-methyl, butamifos, bensulide, piperophos, anilofos,glyphosate, glufosinate, glufosinate-P, and bialaphos.

-   (9) Carbamate Herbicidal Compounds:

di-allate, tri-allate, EPTC, butylate, benthiocarb, esprocarb, molinate,dimepiperate, swep, chlorpropham, phenmedipham, phenisopham,pyributicarb, and asulam.

-   (10) Acid Amide Herbicidal Compounds:

propanil, propyzamide, bromobutide, and etobenzanid.

-   (11) Chloroacetanilide Herbicidal Compounds:

acetochlor, alachlor, butachlor, dimethenamid, propachlor, metazachlor,metolachlor, pretilachlor, thenylchlor, and pethoxamid.

-   (12) Diphenylether Herbicidal Compounds:

acifluorfen-sodium, bifenox, oxyfluorfen, lactofen, fomesafen,chlomethoxynil, and aclonifen.

-   (13) Cyclic Imide Herbicidal Compounds:

oxadiazon, cinidon-ethyl, carfentrazone-ethyl, surfentrazone,flumiclorac-pentyl, flumioxazin, pyraflufen-ethyl, oxadiargyl,pentoxazone, fluthiacet-methyl, butafenacil, benzfendizone,bencarbazone, and saflufenacil.

-   (14) Pyrazole Herbicidal Compounds:

benzofenap, pyrazolate, pyrazoxyfen, topramezone, and pyrasulfotole.

-   (15) Triketone Herbicidal Compounds:

isoxaflutole, benzobicyclon, sulcotrione, mesotrione, tembotrione, andtefuryltrione.

-   (16) Aryloxy Phenoxypropionic Acid Herbicidal Compounds:

clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl,fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl, andquizalofop-ethyl, metamifop.

-   (17) Trione Oxime Herbicidal Compounds:

alloxydim-sodium, sethoxydim, butroxydim, clethodim, cloproxydim,cycloxydim, tepraloxydim, tralkoxydim, and profoxydim.

-   (18) Sulfonylurea herbicidal compounds:

chlorsulfuron, sulfometuron-methyl, metsulfuron-methyl,chlorimuron-ethyl, tribenuron-methyl, triasulfuron, bensulfuron-methyl,thifensulfuron-methyl, pyrazosulfuron-ethyl, primisulfuron-methyl,nicosulfuron, amidosulfuron, cinosulfuron, imazosulfuron, rimsulfuron,halosulfuron-methyl, prosulfuron, ethametsulfuron-methyl,triflusulfuron-methyl, flazasulfuron, cyclosulfamuron, flupyrsulfuron,sulfosulfuron, azimsulfuron, ethoxysulfuron, oxasulfuron,iodosulfuron-methyl-sodium, foramsulfuron, mesosulfuron-methyl,trifloxysulfuron, tritosulfuron, orthosulfamuron, flucetosulfuron, andpropyrisulfuron.

-   (19) Imidazolinone Herbicidal Compounds:

imazamethabenz-methyl, imazamethapyr, imazamox, imazapyr, imazaquin, andimazethapyr.

-   (20) Sulfonamide Herbicidal Compounds:

flumetsulam, metosulam, diclosulam, florasulam, cloransulam-methyl,penoxsulam, and pyroxsulam.

-   (21) Pyrimidinyl Oxybenzoic Acid Herbicidal Compounds:

pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl, pyribenzoxim,pyriftalid, and pyrimisulfan.

-   (22) Other Herbicidal Compounds:

bentazon, bromacil, terbacil, chlorthiamid, isoxaben, dinoseb, amitrole,cinmethylin, tridiphane, dalapon, diflufenzopyr-sodium, dithiopyr,thiazopyr, flucarbazone-sodium, propoxycarbazone-sodium, mefenacet,flufenacet, fentrazamide, cafenstrole, indanofan, oxaziclomefone,benfuresate, ACN, pyridate, chloridazon, norflurazon, flurtamone,diflufenican, picolinafen, beflubutamid, clomazone, amicarbazone,pinoxaden, pyraclonil, pyroxasulfone, thiencarbazone-methyl,aminocyclopyrachlor, ipfencarbazone, and methiozolin.

Active Ingredients of Synergists

piperonyl butoxide, sesamex, sulfoxide,N-(2-ethylhexyl)-8,9,10-trinorborn-5-ene-2,3-dicarboximide (MGK264),N-declyimidazole, WARF-antiresistant, TBPT, TPP, IBP, PSCP, methyliodide (CH₃I), t-phenylbutenone, diethylmaleate, DMC, FDMC, ETP, andETN.

Active Ingredients of Safeners

benoxacor, cloquintocet, cloquintocet-mexyl, cyometrinil,cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole,fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole,isoxadifen, isoxadifen-ethyl, mefenpyr, mefenpyr-diethyl, mephenate,naphthalic anhydride, and oxabetrinil.

Active Ingredients of Plant Growth Regulators

chlormequat-chloride, ethephon, gibberellins (for example, GibberellinA3), hymexazol, inabenfide, mepiquat-chloride, 1-methylcyclopropene,paclobutrazol, prohexadione, prohexadione-calcium, trinexapac,trinexapac-ethyl, uniconazole, uniconazole-P,4-oxo-4-(2-phenylethyl)aminobutyric acid, and methyl5-(trifluoromethyl)benzo[b]thiophene-2-carboxylate.

EXAMPLES

The following Examples serve to illustrate the present invention more indetail, which should not intend to limit the present invention.

Example 1

2-propanol (6.3 parts by weight) was added to a separable flask, andwarmed to 73° C. Type 1 crystals (1 part by weight) were added to theseparable flask at 73° C., and the resulting mixture was stirred tocompletely dissolve the crystals. The temperature of the resultingsolution was lowered at the rate of 3° C./hr under stirring, and thencrystals began to precipitate at 67° C., and the temperature was furtherlowered to room temperature, and the solids were collected from theresulting mixture by filtration to give type 2 crystals.

The resulting type 2 crystals showed the diffraction peaks in powderX-ray diffraction using Cu-Kα radiation as shown in Table 2.

TABLE 2 2θ value (°) d value (Å) Relative intensity (%) 14.0 6.3197 51.414.3 6.2057 100 16.5 5.368 25.1 16.9 5.2423 38.5 17.6 5.0404 21.2 18.84.721 39 19.9 4.4667 82.7 22.3 3.9796 22.3

Example 2

A mixture of xylene (16.0 parts by weight) and n-heptane (16.0 parts byweight) was added to a separable flask, and warmed to 75° C. Type 1crystals (1 part by weight) were added to the separable flask at 75° C.,and the resulting mixture was stirred to completely dissolve thecrystals. The temperature of the resulting mixture was lowered at therate of 5° C./hr under stirring, and a seed crystal of type 2 crystalwas added thereto when the temperature of the solution was 55° C. Then,crystals began to precipitate from the solution, and the temperature ofthe mixture was lowered at the rate of 5° C./hr under stirring to roomtemperature. The solids were collected from the resulting mixture byfiltration to give the type 2 crystals.

For reference, preparation examples of crystals of the Compound (1)which are different from the type 1 crystal and the type 2 crystal aredescribed as Reference Examples. These crystals are all less stable thanthe type 2 crystal.

Reference Example 1

To type 1 crystals (1 part by weight) was added methanol (25 parts byweight) at room temperature to dissolve the crystals. The resultingsolution was left to stand at room temperature for about 1 day to allowmethanol to gradually evaporate, and the resulting solids were filteredto give crystals (hereinafter referred to as “type 3 crystals”).

The resulting type 3 crystals showed the diffraction peaks in powderX-ray diffraction using Cu-Kα radiation as shown in Table 3.

TABLE 3 2θ value (°) d value (Å) Relative intensity (%) 14.5 6.0952 45.315.8 5.6117 33.6 16.2 5.4735 27.6 16.8 5.2603 26.6 18.2 4.8597 67.5 19.14.6381 37.8 19.9 4.4668 100 22.2 3.9974 45.7 23.9 3.7261 27.8 25.93.4372 33.9 27.5 3.2361 80.2 29.9 2.9839 43.6

Reference Example 2

To type 1 crystals (1 part by weight) was added methyl t-butyl ether (60parts by weight) at room temperature to dissolve the crystals. Theresulting solution was left to stand at room temperature for about 1 dayto allow methyl t-butyl ether to gradually evaporate, and the resultingsolids were filtered to give crystals (hereinafter referred to as “type4 crystals”).

The resulting type 4 crystals showed diffraction peaks in powder X-raydiffraction using Cu-Kα radiation as shown in Table 4.

TABLE 4 2θ value (°) d value (Å) Relative intensity (%) 10.9 8.1257 24.412.8 6.9316 60.5 14.7 6.0371 33.1 16.4 5.4137 64.9 16.8 5.2671 63.3 19.74.4984 100 21.4 4.1527 99.2 22.6 3.9379 35.5 24.0 3.6989 24.3 26.23.3961 45.2 31.4 2.85 33.9

Reference Example 3

To xylene (5.0 parts by weight) was added type 1 crystals (1 part byweight) at 65° C. to dissolve the crystals. The resulting solution wasadded dropwise to n-heptane (5.0 parts by weight) at 25° C. toprecipitate solids. After the whole amount of the solution was addeddropwise, the resulting mixture was cooled to room temperature understirring, and the precipitated solids were filtered to give crystals(hereinafter referred to as “type 5 crystals”).

The resulting type 5 crystals showed the diffraction peaks in powderX-ray diffraction using Cu-Kα radiation as shown in Table 5.

TABLE 5 2θ value (°) d value (Å) Relative intensity (%) 8.0 11.0092 28.813.8 6.4018 26.0 14.4 6.1623 82.2 14.9 5.9219 29.7 15.1 5.8709 63.0 16.75.3167 77.9 17.8 4.9781 59.2 18.0 4.9203 30.3 18.5 4.7950 29.8 19.54.5381 63.3 20.0 4.4399 100.0 22.7 3.9148 56.2 25.2 3.5255 56.5 30.62.9203 40.4

Next, Formulation examples of the present pesticide formulation areshown below.

Formulation Example 1

Type 2 crystals (20 parts by weight), sodium lauryl sulfate (4 parts byweight), calcium lignin sulfonate (2 parts by weight), silica finepowder (20 parts by weight), and diatomaceous earth (54 parts by weight)are mixed to obtain a 20% wettable powder.

Formulation Example 2

Type 2 crystals (2 parts by weight), silica fine powder (1 part byweight), calcium lignin sulfonate (2 parts by weight), bentonite (30parts by weight), and kaolin (65 parts by weight) are mixed. To theresulting mixture is added an appropriate amount of water, and theresulting mixture is kneaded. The resulting kneaded product is subjectedto extruding granulation with a granulator and forced-air drying toobtain a 2% granule.

Formulation Example 3

Type 2 crystals (2 parts by weight), a binder (5 parts by weight), anon-ionic surfactant (1 part by weight), and pyrophyllite clay (92 partsby weight) were mixed. To the resulting mixture was added an appropriateamount of water, and the resulting mixture was kneaded. The resultingkneaded product was subjected to extruding granulation with a baskettype granulator and forced-air drying to obtain a 2% granule having φ1.2mm.

Formulation Example 4

A mixture of polyoxyethylene alkyl ether sulfate ammonium salt and whitecarbon (weight ratio of 1:1) (35 parts by weight), type 2 crystals (10parts by weight), and water (55 parts by weight) are fully mixed toobtain a 10% flowable formulation.

Next, the control efficacies against pests of the present pesticideformulation are shown below.

Test Example 1

The 2% granule comprising the type 2 crystals obtained in theFormulation example 3 (hereinafter referred to as “present granule 1”)and a 2% granule obtained according to the Formulation example 3 byusing type 1 crystals instead of the type 2 crystals (hereinafterreferred to as “comparative granule 1”) were prepared.

To the plant foot soil of one stock of rice seedling (Oryza sativa,cultivar: Hinohikari) with 2.5 leaf stage planted in a cell tray with200 holes was applied the present granule 1 or the comparative granule 1(50 mg), and then ion exchanged water (0.5 ml) was added dropwisethereto. After being left to stand in a room for 1.5 hours, the riceseedling and the soil in the cell tray were transplanted into a Wagnerpot (area: 1/5000a) containing flooded soil, and grown in a greenhouse(25° C.). After 50 days from the transplantation, the whole rice wascovered with a nylon gauze, and brown planthoppers (Nilaparvata lugens)(6 heads of female 5th instar larvae just before eclosion and 3 heads ofmale adults just before eclosion per one pot) were released thereto.After 24 days from the release of the brown planthoppers, the number ofthe eclosed larvae lived on the rice was investigated (hereinafterreferred to as “test group”).

A rice seedling was grown in a similar manner to the test group exceptthat treatment with the granule comprising the Compound (1) was notmade. After 50 days from the transplantation, brown planthoppers werereleased to the rice like the test group, and the number of the eclosedlarvae lived on the rice was investigated (hereinafter referred to as“control group”).

Control effect was calculated according to the following equation on thebasis of the observations in the test group and the control group (eachtest was carried out 3 iterations, and the average value wascalculated).Control effect (%)=100−(number of insects in test group/number ofinsects in control group)×100

TABLE 6 Granule Control effect (%) Present granule 1 100 Comparativegranule 1 85

INDUSTRIAL APPLICABILITY

The type 2 crystal is a stable crystal of2-(3-ethanesulfonylpyridin-2-yl)-5-(trifluoromethanesulfonyl)benzoxazole,and may be used for controlling pests.

The invention claimed is:
 1. A type 2 crystal of2-(3-ethanesulfonylpyridin-2-yl)-5-(trifluoromethanesulfonyl)benzoxazole,wherein the crystal has diffraction peaks at 2θ=14.0±0.2°, 14.3±0.2°,16.5±0.2°, 16.9±0.2°, 17.6±0.2°, 18.8±0.2°, 19.9±0.2°, and 22.3±0.2° inpowder X-ray diffraction using Cu-Kα radiation.
 2. A pesticideformulation comprising the type 2 crystal according to claim 1 as anactive ingredient.
 3. A method for producing the type 2 crystalaccording to claim 1 wherein the method comprises dissolving a type 1crystal of2-(3-ethanesulfonylpyridin-2-yl)-5-(trifluoromethanesulfonyl)benzoxazolehaving diffraction peaks at 2θ=13.7±0.2°, 16.2±0.2°, 16.6±0.2°,17.1±0.2°, 18.8±0.2°, 20.2±0.2°, 21.4±0.2°, and 27.6±0.2° in powderX-ray diffraction using Cu-Kα radiation into 2-propanol, andprecipitating the type 2 crystal at a temperature of 65 to 67° C.